Process for producing durable mechanical effects on cellulose fabrics by applying acetals and products resulting therefrom



U ited States Paten PROCESS FOR PRODUCING DURABLE MECHANI- CAL; EFFECTS ON CELLULOSE-EABRICS -BY'AP- PLYING ACETALS AND PRODUCTS RESULTING THEREFROM Bernard Kress, Ambler, t and-Ellis #Abrams, Philadelphia, Pal, assignors to Quaker Chemical Products Corporation Conshohocken, Pa., a corporation of-Pennsylvania No Drawing. Application February 19, 1954, Serial No. 411,542

13 Claims. (Cl. 8-116) This" invention 'relates to thetreatment" of textile materials containing a substantial quantity of cellulose for the purpose of obtaining a variety ofmechanical effects which-are durable to laundering and dry cleaning.

This invention provides a new process for treating cellulosic textile materials in order to obtain such mechanical effects as can be obtained by various types of calendering. Glazed, embossed, Shreinered, chased, and moir fabrics are among the types which can be produced by this-new process. In general, the fabrics produced according to this invention are spot, soil, and crease resistant, stretch and shrink resistant, launderable by washing or dry cleaning, quick drying,:ironable, and long wearing It is well-known in the art to obtain durablemechanical effects on cellulosicfabrics by impregnating .-same i in aqueous solutions of thermosetting resins and acidic or potentially acidic catalysts. The impregnated fabrics are then dried at a relatively low temperature to a moisture content of about 10% and subsequently subjected to. some type of hot calendering operation such as a glazer where the top roll travels more rapidly than the bottom roll. This operation glazes and partially sets the resin. Finally the fabric is passed through a curing oven operated at 300-400- F. for a period of about one-half to minutes, the length of time varying inversely with the temperature of cure'. Among the materials which have been recommended for this operation are urea-formaldehyde resins, thio-urea formaldehyde resins, melamine formaldehyde resins and various modified urea-formaldehyde resins.

All of the aforesaid materials which have been recommended as aids in setting the mechanical effects have several properties in common which differentiate them from the' materials to be discussed in this invention.- The materials hitherto known to the art are all thermosetting resin-forming products. When these materials are heated in an oven at 300 F. in presence of an acidic catalyst,

they 'arefconverted to infusible products. Moreover," these materials are potential film formers. It has also been observed that these' materials possess the unfortunate property of retaining chlorine to some degree when-"they are bleached with chlorine containing bleaches *as might occur during home or commercial laundering operations. This factor limits the utility of fabrics treated with these materials by imposing conditions of special handling during laundering.

Another factor whichjimposes limitations-on treat- In other instances objectionable odors maydevelop in the" fabric after finishing. Furthermore, it has been observed "that the degree of durability to launderingobtained through. the use ofthese condensates is rather limited.

In view of the present state of the art, it is indeed \inice expected and surprising that durable washfast mechanical finishes can be'obtained by treating textile fabrics :with non-resin: forming materials prior to calendering and curmg.

Anobject of this invention'is to obtain :durable mechanical efiects on cellulosic fabrics which will be free from the danger of chlorine retention due to bleaching. Incidental to these efiects,-we also aim to obtain fabrics which are resistant to spotting, soiling, and'fraying and which possess improved .creaseresistance and substantial retention of tear and tensile strength.

A further objectof this inventionis to provide a treatment which will impart a minimum degree of discoloration-to the-treated fabric. Further, the treated material will b'efree of objectionable odors or the disposition:. to form disagreeable odors. Moreover, the padding, drying, andcuringoperations will be substantially free of odors.

Further advantages of the invention will become. apparent-from the detailed description of the discovery which follows.

It has been discovered that the above-mentionedobjects may beaccomplished by treating cellulosic textile materials, prior todrying, calendering, and curing, with non-volatile acetals of monoaldehydes and dialdehydes containing up to eight carbon atoms in the presence of an acidic catalyst; The term non-volatile" as applied hererefers to non-volatility at the curing temperature of at least 250'F. In using the acetals according to this invention, at no time during the padding, drying, calenderr ing,.-or curing operations is there a detectable odor of aldehyde. This is especially significant in the case of the acetals of formaldehyde.

Suitable aldehydes which may be converted to acetals in this process are formaldehyde, acetaldehyde, propanal, butanal, glyoxal, and other monoand dialdehydes containing not more than eight carbon atoms in the monomeric form, such as -malonaldehyde, succinaldehyde, glutaraldehyde, adipaldehyde, hydroxyadipaldehyde, benzaldehyde, terephthalaldehyde, and the like.

Suitable alcoholswhich may be reacted with the abovementioned aldehydes to form acetals are methanol, ethanol, propanol, isopropanol, butanol, methoxyethanol, ethoxyethanol, methoxyethoxyethanol, ethylene glycol, a propylene glycol, a butylene glycol, diethylene glycol, ,dipropylene. glycol, dibutylene glycols and higher dialkylene glycols, polyalkylene glycols, polyhydric alcohols such as glycerine, mannitol and sorbitol, and glycol monoethers and partial ethers ofpolyhydric alcohols.

Inco-pending, applications, Serial Numbers 403,078 filed January 8, 1954, and 403,057, filed January 8, 1954, we have disclosed individually that both monomeric acetals andpolymeric acetals may be used in the presence of acidic-catalysts for purposes of dimensional control of cellulosic textile materials. We now find that these various acetalsmaypbe used to achieve the objects of .this invention. 1

Suitable monomeric acetals applicable in this process are di-(hydroxyethoxyethyl) formal, di-(methoxyethoxyethyl) formal, di-(methoxyethyl) formal, di-(hydroxyethyl) formal, malonaldehyde tetra-(methoxyethyl) acetal, glyoxal tetramethyl acetal, glyoxal tetraethyl acetal, glyoxal tetrabutylzacetal, Z-hydroxyadipaldehyd tetra-(methoxyethyl) acetal and mixed acetals such as methyl methoxyethyl formal, malonaldehyde methyl triethyl acetal, glyoxaldibutyl dimethoxyethyl acetal, dimethoxymethoxyethyl ether, or methyl hydroxyethoxyethyl formal or mixtures thereof. In general, the acetals are "prepared by reacting the aldehydes and alcohols in the'presence of acidic catalysts bywell-known procedures. Mixed acetals maybe prepared by reactingthe, aldehyde with a mixture of the alcohols or by carrying out an exchange reaction between a given acetal and the desired alcohol.

In general, our preferred monomeric acetals have boiling points above 125 C. and are derived from aldehydes containing one to eight carbon atoms and hydroxyl-bearing compounds containing at least one alkyl or alkylene radical, i. e. at least one continuous carbon chain possessing from one to six carbon atoms.

The polymeric acetals which are applicable in this invention are reaction products between an aldehyde and an alkylene or polyalkylene glycol. Typical polymeric acetals may be prepared from diethylene glycol and formaldehyde, ethylene glycol and formaldehyde, diethylene glycol, formaldehyde and glyoxal, diethylene glycol, sorbitol and formaldehyde, diethylene glycol and acetaldehyde, dipropylene glycol and hydroxyadipaldehyde and the like.

In general, those polymeric acetals which have proved useful in this invention may be made starting with ethyl- Y ene glycol, a propylene glycol, a butylene glycol, dipropylene glycol, dibutylene glycols, and higher dialkylene glycols, polyalkylene glycols, mixtures thereof, or their mixtures with diethylene glycol which are reactive with formaldehyde or other aldehydes to form water soluble products or products which are dispersible in water, either alone or with the aid of appropriate adjuvants. Polyalkylene glycols, such as triethylene glycol, tetraethylene glycol, tripropylene glycol and the like may also be used, either alone or in admixture with the aforementioned glycols. Likewise polyols, such as glycerine, pentaerythritol and sorbitol, may be added to the alkylene glycols in amounts up to about 50 mole percent of the glycols for reaction with the aldehyde for forming water soluble or water dispersible products. Various materials, such as paraform-aldehyde, formalin, trioxane, or methylal may be used as sources of formaldehyde. Other suitable aldehydes have been mentioned above and mixtures of these may be used in forming the condensation products. The term alkylene is understood to include a doubly unsatisfied aliphatic radical containing a substituted or unsubstituted straight chain possessing from two to four carbon atoms in the chain and having its unsatisfied valences on either adjacent or separated carbon atoms. If desired, the chains of the polymeric compounds may be terminated, either in whole or in part, by means of an alkyl radical possessing not more than eight carbon atoms.

Those of our acetals which are water soluble are applied to fabric with acidic catalysts from aqueous solutions. from isopropanol solutions or from oil in water emulsions. In all cases, excellent retention of the mechanical deformation was obtained, no chlorine retention was observed and no obnoxious odors were noted during any of 3 a linear polymeric structure.

The water insoluble acetals were applied either i of the acetal. The padding bath must contain additionally some acidic-type catalyst, such as zinc chloride, maleic anhydride, oxalic acid, ammoniumlchloride, ammonium thiocyanate, citric acid, tartaric acid, phosphoric acid, ethyl acid phosphate, ammonium sulfate, sodium bisulfate, etc., in amount of about 5 to 200% by weight to some suitable type of'calendering at about 350 to 400 one plain roll. A linen-like effect may, be produced by chasing and a moir efiect can be obtained with specially engraved rolls. In any event, the calendering is carried out at elevated temperature and at pressures approximating 5 tons per square inch. Subsequent to the calendering operation, the fabric is cured at a temperature of at least 250 F. for about A. to 10 minutes. The time of the cure varies inversely with the temperature. The cured fabric may then be washed lightly with a detergent and a mild alkali, rinsed thoroughly and dried.

The following illustrative examples will serve to explain our invention. Example I below illustrates the prepartion of a typical polyformal as described in copending application, Serial Number 403,056 filed January Example I Diethylene glycol moles.. 1 Paraformaldehyde -do-.. 1 Sulfuric acid do 0.001 Toluene ml 25 The above components are mixed and heated under reflux in an apparatus equipped with a water trap. The solution is refluxed and water removed by azeotropic distillation. When 1 mole of water of reaction is removed the desired reaction is complete. The reaction mixture is neutralized with dilute sodium hydroxide solution and toluene is removed by evaporation in vacuo at temperatures not exceeding C. The product is a viscous liquid, setting to a crystalline mass below 16 C. It is completely water soluble and also soluble in toluene and esters. The product has a molecular weight of 480 (Rast) and a hydroxyl equivalent of 220 which indicates it has It has a specific gravity of 1.155 at 94 F. The refractive index is N :1.462. The molecular weight and hydroxyl equivalent of the condensation product of this example indicate that this product possesses a polymeric structure, containing an average of four diethylene glycol units, as shown in the following formula:

where X and Y may be either H or CH2OH. Similarly, monofunctional alcohol modified, condensation products may be prepared as in Example 11.

Example 11 Parts Diethylene glycol v 101 Beta methoxyethanol 4 Paraformaldehyde (91%) 30 Toluene 20 Sulfuric acid (99%) 0.1

The above materials were reacted as in Example I to yield a viscous liquid possessing a faint ethereal odor and soluble in water. -Its polymeric nature was shown by Rast molecular weight determination which had a value of 63 7.

Similarly polyols may modify the polymeric condensation product.

7 Example III 7 These reactants were treated as in Example I. The product was a crystalline mass at room temperature, soluble in toluene and in Water, and virtually no odor.

The application of acetals is illustrated by the following examples.

n Example IV An aqueous solutionis prepared containing the following:

. Percent Product of Example I"; 7.5 Ammonium chloride 0.8

The solution was padded on 80x 80 cotton sheeting at 100'percent pickup. The fabric was dried at 180 F. until it reached a moisture content of 11% and then calendered through heated rolls at 400 F. and under a pressure of aboutS tons per square inch. The fabric was then curedat 300 F. for 5 minutes and finally washed and dried. The fabric possessed a lustrous finish which was substantially retained even after soaping at the boil for minutes. The crease resistance was substantially improved and the retention of tear and tensile strength was good. Chlorine retention tests conducted according to American'Association of Textile Chemists and Colorists (AL A. T. C. C. 1952) tentative specification-69 52 showed no effects due to retained chlorine. A test with warm 5% sodium carbonate solution showed no indication of residual odor in the fabric.

Example V A solution containing the following materials was prepared:

Percent Dimethoxyethyl formal 10 Oxalic acid 1.0

Cotton sheeting (80 x 80) was treated as described in Example IV. The results were substantially the same as in Example IV.

Example VI An aqueous solution was prepared by dissolving the following materials:

Percent Product of Example I 7.5 Zinc chlorid 2.0

Cotton sheeting (80 x 80) was treated as in ExampleIV. The material possessed a soft hand and a deep lustrous appearance.

Example VII An aqueous solution containing the following materials was prepared:

Percent Condensation product of Example I 7.5 Polyvinyl alcohol 0.5 Maleic anhydride 0.5

Cotton sheeting 80 x 80 was treated as in Example IV. The treated fabric possessed a deep lustrous appearance and increased crispness over that shown in Example V.

Example VIII An aqueous impregnation bath was prepared containing the following materials:

Percent Condensation product of Example I 10.5 Polyvinyl alcohol 0.75 Oxalic acid 4.0

Example IX Pounds Condensation product of Example 1-". Polyvinyl alcohol 7.5 Ammonium chloridei 17.0

Water to make gallonsj Example X I The following solution was "prepared:

Percent Glyoxal tetramethoxyethyl' acetal 10 Oxalic acid .1 Water 7 85 The acetal was prepared according to directions given in U. S. Patent 2,321,094. The solution was usedto impregnate 80 x 80 cotton sheeting as described in Example IV. A durably glazed-fabric was obtained Example XI The following solution was prepared:

Percent Glyoxal' tetramethoxyethyl acetal 10 oxalic acid 1.5 Water 86.5

This solution was applied to 80 :x 80 cotton sheetingas in Example IV with similar results.

Example XII A solution was preparedcontainingthe following:

Percent Product of Example II 7.5 Polyvinyl alcohol 0.5 Zinc chloride 2.0 Water 90.0

This solution was used-to impregnatecotton sheeting (80 x 96) as described in Example IV. The fabric was dried on a tenter frame to a moisture content of 11.5 and passed through specially engraved calender rolls at 375 F. to produce a moir effect. The'fabric was then cured at 400 F. for 30 seconds, washed and dried. The pattern retention on repeated laundering was excellent. Noobjectionable odors were noticed during the operations and the fabric showed no effects due to chlorine retention.

Example XIII The following solution was applied 'to cotton sheeting 80 x 80 as described in Example XII and with similar results:

Percent Product of Example III 8.0 Oxalic acid 0.8 Water 89.0

The term cellulose textile material is intended to include fabrics, whether knitted, woven or felted, consisting of natural cellulose, regenerated cellulose, such as viscose rayon, cuprammonium rayon, and hydrolized cellulose acetate and mixtures thereof. Also included are fabric blends containing a preponderance of cellulosic type components.

The invention herein described is useful in a wide range of mechanical finishing operations. While we have de' --7 scribed several of these procedures, our invention is not limited thereto but is applicable to any operation wherein it is desired to cause a mechanical surface deformation of a textile material to beco me durable to laundering. In the appended claims, therefore, we do not intend to restrict ourselves to the specific methods and conditions given above as illustrative; by the term physically modifying therein employed we mean that result of modification of the surface of a textile material by any appropriate mechanical means and under any suitable conditions of time, temperature, and pressure to impart to the surface a distinctive appearance, such as moir, wave, crepe, stamping, lucid gloss, matted gloss, silk lustre, imitation mercerizing and various other surface effects and designs.

We claim:

1. The process of modifying the surface appearance of a cellulose textile material which comprises applying to a cellulose textile material an aqueous bath containing an acidic catalyst and an acetal of an aldehyde selected from the group consisting of aliphatic and carbocyclic aldehydcs having 1 to 8 carbon atoms in monomeric form and mixtures of the aforesaid aldehydes, and an aliphatic hydroxyl-bearing compound selected from the group consisting of aliphatic monohydric alcohols containing from 1 to 5 carbon atoms, monoalkylene and polyalkylene glycols in which the alkylene radical has from 2 to 4 carbon atoms in a straight chain, and aliphatic polyhydric alcohols containing from 3 to 6 hydroxyl groups and from 3 to 6 carbon atoms and mixtures of the aforesaid aliphatic hydroxyl-bearing compounds, said acetal having a boiling point above about 125 C., said catalyst being present in amount from about 5% to about 200% by weight of the acetal content in said bath and said acetal being present in amount from about 2% to about 25% by weight of the bath, modifying the surface'appearance of the treated textile material by applying pressure thereto and heating the textile material at an elevated temperature until the cellulose and acetal react and the surface appearance of the textile material is modified and stabilized to laundermg.

2. The process of modifying the surface appearance of a cellulose textile material which comprises applying to a cellulose textile material an aqueous bath containing an acidic catalyst and an acetal of an aldehyde selected from the group consisting of aliphatic and carbocyclic aldehydes having 1 to 8 carbon atoms in monomeric form and mixtures of the aforesaid aldehydes, and an aliphatic hydroxyl-bearing compound selected from the group consisting of aliphatic monohydric alcohols containing from 1 to 5 carbon atoms, monoalkylene and polyalkylene glycols in which the alkylene radical has from 2 to 4 carbon atoms in a straight chain, and aliphatic polyhydric alcohols containing from 3 to 6 hydroxyl groups and from 3 to 6 carbon atoms and mixtures of the aforesaid aliphatic hydroxyl-bearing compounds, said acetal having a boiling point above about 125 C., said catalyst being present in amount from about 5% to about 200% by weight of the acetal content in said bath and said acetal being present in amount from about 2% to about 25% by weight of the bath, modifying the surface appearance of the treated textile material by applying pressure thereto and heating the textile material at a temperature of at least about 250 F. for about /2 to 10 minutes until the cellulose and acetal react and the surface appearance of the textile material is modified and stabilized to laundering,

3. The process of modifying the surafce appearance of a cellulose textile material as defined in claim 1 wherein the bath contains an acetal of diethylene glycol and formaldehyde. 7

4. The process of modifying the surface appearance of a cellulose textile material as defined in claim 1 wherein the acetal in the aqueous bath is the condensation product of diethylene glycol, sorbitol and formaldehyde.

5. The process of modifying the surface appearance of a cellulose textile material as defined in claim 1 wherein the acetal in the aqueous bath is di-(methoxyethyl) formal.

6. The process of modifying the surface appearance of a cellulose textile material as defined in claim 1 wherein the acetal in the aqueous bath is malonaldehyde methyl triethyl acetal.

7. The process of modifying the surface appearance of a cellulose textile material as defined in claim 1 wherein the acetal in the aqueous bath is glyoxal tetra-(methoxyethyl) acetal.

8. Cellulose textile material having a durable surface appearance resisting laundering made by the process of claim 1.

9. Cellulose textile material having a durable surface appearance resisting laundering made by the process of claimi3.

10. Cellulose textile material having a durable surface appearance resisting laundering made by the process of claim 4.

11. Cellulose textile material having a durable surface appearance resisting laundering made-by the process of claim 5.

l2. Cellulose textile material having a durable surface appearance resisting laundering made by the process of claim 6.

l3. Cellulose textile material having a duarble surface appearance resisting laundering made by the process of claim 7.

References Cited in the file of this patent UNITED STATES PATENTS OTHER REFERENCES Marsh, John T.: An Introduction to Textile Finishing, 1948, p. 381, 

1. THE PROCESS OF MODIFYING THE SURFACE APPEARANCE OF A CELLULOSE TEXTILE MATERIAL WHICH COMPRISES APPLYING TO A CELLULOSE TEXTILE MATERIAL AN AQUEOUS BATH CONTAINING AN ACIDIC CATALYST AND AN ACETAL OF AN ALDEHYDE SELECTED FROM THE GROUP CONSISTING OF ALIPHATIC AND CARBOCYCLIC ALDEHYDES HAVING 1 TO 8 CARBON ATOMS IN MONOMERIC FORM AND MIXTURES OF THE AFORESAID ALDEHYDES, AND AN ALIPHATIC HYDROXYL-BEARING COMPOUND SELECTED FROM THE GROUP CONSISTING OF ALIPHATIC MONOHYDRIC ALCOHOLS CONTAINING FROM 1 TO 5 CARBON ATOMS, MONOALKYLENE AND POLYALKYLENE GLYCOLS IN WHICH THE ALKYLENE RADICAL HAS FROM 2 TO 4 CARBON ATOMS IN A STRAIGHT CHAIN, AND ALIPHATIC POLYHYDRIC ALCOHOLS CONTAINING FROM 3 TO 6 HYDROXYL GROUPS AND FROM 3 TO 6 CARBON ATOMS AND MIXTURES OF THE ADORESAID ALIPHATIC HYDROXYL-BEARING COMPOUNDS, SAID ACETAL HAVING A BOILING POINT ABOVE ABOUT 125*C., SAID CATALYST BEING PRESENT IN AMOUNT FROM ABOUT 5% TO ABOUT 200% BY WEIGHT OF THE ACETAL CONTENT IN SAID BATH AND SAID ACETAL BEING PRESENT IN AMOUNT FROM ABOUT 2% TO ABOUT 25% BY WEIGHT OF THE BATH, MODIFYING THE SURFACE APPEARANCE OF THE TREATED TEXTILE MATERIAL BY APPLYING PRESSURE THERETO AND HEATING THE TEXTILE MATERIAL AT AN ELEVATED TEMPERATURE UNTIL THE CELLULOSE AND ACETAL REACT AND THE SURFACE APPEARANCE OF THE TEXTILE MATERIAL IS MODIFIED AND STABILIZED TO LAUNDERING. 